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Synthetic method of aryl halide taking aryl carboxylic acid as raw material

A technology of aryl halides and synthesis methods, which is applied in the field of synthesis and preparation of chemical products, can solve the problems of large amount of cuprous salt, etc., and achieve the effects of small amount, good tolerance, and high yield

Active Publication Date: 2017-11-07
NANCHANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0014] Although this method synthesizes aryl chlorides, bromides and iodides well by decarboxylation of aryl carboxylic acids, there is too much amount of cuprous salt in the reaction, and the halogen source comes from the more expensive cuprous halide

Method used

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  • Synthetic method of aryl halide taking aryl carboxylic acid as raw material
  • Synthetic method of aryl halide taking aryl carboxylic acid as raw material
  • Synthetic method of aryl halide taking aryl carboxylic acid as raw material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Example 1. Synthesis of 2-nitro-4-chloroiodobenzene.

[0054] Add 6.2 mg of silver sulfate, 21.8 mg of copper acetate, 12.5 mg of 2,9-dimethyl-1,10-phenanthroline, 2-nitro-4-chloro Benzoic acid 40.3 mg, sodium iodide 45 mg and 4 mL of dimethyl sulfoxide. Heated at 160°C for 24 hours in the presence of oxygen. After the reaction was completed, distilled water was added to quench the reaction, and ethyl acetate was used to extract 3 times, 10 mL each time, and the combined organic phase was concentrated to obtain 40.8 mg of 2-nitro-4-chloroiodobenzene, with a yield of 72%. .

[0055] Product 2-nitro-4-chloroiodobenzene: 1 H NMR (400MHz, CDCl 3 ): δ7.95(d, J=8.5Hz, 1H), 7.84(d, J=2.0Hz, 1H), 7.28-7.25(m, 1H); 13 C NMR (100MHz, CDCl 3 ): δ142.7, 135.3, 133.6, 125.7, 83.6.

Embodiment 2

[0056] Example 2. Synthesis of 2-nitro-4-chlorobromobenzene.

[0057] Add 6.2 mg of silver sulfate, 36.3 mg of copper acetate, 12.5 mg of 2,9-dimethyl-1,10-phenanthroline, 2-nitro-4-chloro Benzoic acid 40.3 mg, sodium bromide 30.9 mg and 4 mL of dimethyl sulfoxide. Heated at 160°C for 24 hours in the presence of oxygen. After the reaction was completed, distilled water was added to quench the reaction, and ethyl acetate was used to extract 3 times, 10 mL each time, and the combined organic phase was concentrated to obtain 30.3 mg of 2-nitro-4-chlorobromobenzene, with a yield of 64%. .

[0058] Product 2-nitro-4-chlorobromobenzene: 1 H NMR (400MHz, CDCl 3 ): δ7.85(d, J=2.1Hz, 1H), 7.69(d, J=8.6Hz, 1H), 7.42(dd, J=2.2, 8.5Hz, 1H). 13 C NMR (100MHz, CDCl 3 ): δ135.9, 133.3, 125.8, 112.6.

Embodiment 3

[0059] Example 3. Synthesis of 2-nitro-1,4-dichlorobenzene.

[0060] Add 6.2 mg of silver sulfate, 36.3 mg of copper acetate, 12.5 mg of 2,9-dimethyl-1,10-phenanthroline, 2-nitro-4-chloro Benzoic acid 40.3 mg, sodium chloride 17.5 mg and 4 mL of dimethyl sulfoxide. Heated at 160°C for 24 hours in the presence of oxygen. After the reaction was completed, distilled water was added to quench the reaction, and ethyl acetate was used to extract 3 times, 10 mL each time, and the combined organic phase was concentrated to obtain 20.7 mg of 2-nitro-1,4-dichlorobenzene. The yield was 54%.

[0061] Product 2-nitro-1,4-dichlorobenzene: 1 H NMR (400MHz, CDCl3): δ7.88(s, 1H), 7.50(d, J=0.8Hz, 2H). 13 C NMR (100MHz, CDCl 3 ): δ133.3, 132.8, 125.7.

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Abstract

A synthetic method of an aryl halide taking aryl carboxylic acid as a raw material is characterized in that a corresponding aryl halide is formed by carrying out substitution reaction on an aryl carboxylic acid compound and haloid salt MX in an organic solvent under the condition that oxygen, a silver catalyst, a copper additive and a bidentate nitrogen ligand exist, wherein M in MX represents alkali metal or alkaline earth metal, and X represents F, Cl, Br or I. Compared with a conventional aryl halide synthetic method, the synthetic method disclosed by the invention has the obvious advantages that reaction raw materials (comprising aryl carboxylic acid and MX) are cheap and easy to obtain, the using amount of a metal catalyst is small, pollution to the environment when the oxygen is used as an oxidant is the smallest, good tolerance to various functional groups on an aromatic ring is obtained, the yield is high, and the like. The synthetic method disclosed by the invention can be widely applied to synthesis in the fields of medicine, materials, natural products and the like in industry and academia.

Description

technical field [0001] The present invention relates to the synthesis and preparation of a class of chemical products, more specifically to the synthesis method of aryl halides. Background technique [0002] The introduction of halogen groups (-I, -Br, -Cl, -F, etc.) on aromatic compounds can significantly change the physical, chemical and biological properties of aromatic compounds. Aryl halides are not only important structural units of pharmaceuticals, pigments, liquid crystal materials and other chemical products, but also many natural compounds, and aryl halides are often used as raw materials for organic synthesis reactions to construct C-C bonds and C-heteroatom bonds. Therefore, the synthesis of related aryl halides has important theoretical significance and industrial practical value. Currently, methods for synthesizing aryl halides include: [0003] Method 1, the traditional method of synthesizing aryl halides is in Lewis acid (such as, Fe, FeX 3 etc.), through ...

Claims

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Application Information

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IPC IPC(8): C07C201/12C07C205/12C07C205/37C07C41/22C07C43/225C07D333/62C07D307/82C07B39/00
CPCC07B39/00C07C41/22C07C201/12C07D307/82C07D333/62C07C205/12C07C205/37C07C43/225
Inventor 付拯江蔡琥李兆杰姜李高
Owner NANCHANG UNIV
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